CN105792860B - Reflective soft acrylic material with high refractive index and minimum - Google Patents
Reflective soft acrylic material with high refractive index and minimum Download PDFInfo
- Publication number
- CN105792860B CN105792860B CN201480065465.3A CN201480065465A CN105792860B CN 105792860 B CN105792860 B CN 105792860B CN 201480065465 A CN201480065465 A CN 201480065465A CN 105792860 B CN105792860 B CN 105792860B
- Authority
- CN
- China
- Prior art keywords
- phenyl
- ester
- ethyl ester
- acrylic acid
- methacrylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000463 material Substances 0.000 title claims abstract description 112
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000000178 monomer Substances 0.000 claims abstract description 43
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 36
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 16
- -1 poly(ethylene glycol) Polymers 0.000 claims description 136
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 62
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 47
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 claims description 38
- 125000004494 ethyl ester group Chemical group 0.000 claims description 27
- 229920001223 polyethylene glycol Polymers 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 26
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 claims description 20
- 150000002148 esters Chemical class 0.000 claims description 15
- 239000002250 absorbent Substances 0.000 claims description 14
- 230000002745 absorbent Effects 0.000 claims description 14
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims description 9
- 230000009477 glass transition Effects 0.000 claims description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-butanediol Substances OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 125000006519 CCH3 Chemical group 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- PKBZUGSITIBLFK-UHFFFAOYSA-N 3-phenylpropyl prop-2-enoate Chemical compound C=CC(=O)OCCCC1=CC=CC=C1 PKBZUGSITIBLFK-UHFFFAOYSA-N 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 238000005259 measurement Methods 0.000 claims description 5
- 125000005401 siloxanyl group Chemical group 0.000 claims description 5
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N Trimethylene glycol Natural products OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000975 dye Substances 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 3
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 claims description 3
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- 230000008901 benefit Effects 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 150000001253 acrylic acids Chemical class 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- 239000011521 glass Substances 0.000 claims 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 claims 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 50
- 239000002585 base Substances 0.000 description 45
- 210000000695 crystalline len Anatomy 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 230000002209 hydrophobic effect Effects 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 230000000007 visual effect Effects 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000012964 benzotriazole Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- QYBWIXBVMQYFIL-UHFFFAOYSA-N 2-chlorobenzotriazole Chemical compound C1=CC=CC2=NN(Cl)N=C21 QYBWIXBVMQYFIL-UHFFFAOYSA-N 0.000 description 5
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 5
- 230000003667 anti-reflective effect Effects 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000001118 alkylidene group Chemical group 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 210000004087 cornea Anatomy 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 229910000078 germane Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 3
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 150000002894 organic compounds Chemical group 0.000 description 3
- 208000007578 phototoxic dermatitis Diseases 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OJNXPAPLAAGFBJ-UHFFFAOYSA-N (4-methylphenyl) prop-2-enoate Chemical compound CC1=CC=C(OC(=O)C=C)C=C1 OJNXPAPLAAGFBJ-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- GLSKMRNRRMNAQS-UHFFFAOYSA-N 5-(trifluoromethyl)-2h-benzotriazole Chemical compound C1=C(C(F)(F)F)C=CC2=NNN=C21 GLSKMRNRRMNAQS-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 2
- 230000036760 body temperature Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 125000005641 methacryl group Chemical group 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- VJMJYBVERHZATL-UHFFFAOYSA-N (2,4,6-trimethylbenzoyl)phosphonoyl-(2,4,6-trimethylphenyl)methanone Chemical class CC1=CC(C)=CC(C)=C1C(=O)P(=O)C(=O)C1=C(C)C=C(C)C=C1C VJMJYBVERHZATL-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- RBUACGOFWUSJNX-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-ethenylphenol Chemical compound OC1=CC=C(C=C)C=C1N1N=C2C=CC=CC2=N1 RBUACGOFWUSJNX-UHFFFAOYSA-N 0.000 description 1
- TURITJIWSQEMDB-UHFFFAOYSA-N 2-methyl-n-[(2-methylprop-2-enoylamino)methyl]prop-2-enamide Chemical compound CC(=C)C(=O)NCNC(=O)C(C)=C TURITJIWSQEMDB-UHFFFAOYSA-N 0.000 description 1
- YBKWKURHPIBUEM-UHFFFAOYSA-N 2-methyl-n-[6-(2-methylprop-2-enoylamino)hexyl]prop-2-enamide Chemical compound CC(=C)C(=O)NCCCCCCNC(=O)C(C)=C YBKWKURHPIBUEM-UHFFFAOYSA-N 0.000 description 1
- MTWBNQBGOBEJKB-UHFFFAOYSA-N 2-phenylethoxymethylbenzene Chemical compound C=1C=CC=CC=1COCCC1=CC=CC=C1 MTWBNQBGOBEJKB-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- KARGMXZXPAWXQJ-UHFFFAOYSA-N 3-[3-(benzotriazol-2-yl)-4-hydroxyphenyl]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 KARGMXZXPAWXQJ-UHFFFAOYSA-N 0.000 description 1
- NWBTXZPDTSKZJU-UHFFFAOYSA-N 3-[dimethyl(trimethylsilyloxy)silyl]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](C)(C)O[Si](C)(C)C NWBTXZPDTSKZJU-UHFFFAOYSA-N 0.000 description 1
- FOYKCXMFPGANMJ-UHFFFAOYSA-N 3-ethoxysilylpropyl prop-2-enoate Chemical compound CCO[SiH2]CCCOC(=O)C=C FOYKCXMFPGANMJ-UHFFFAOYSA-N 0.000 description 1
- PZBQVZFITSVHAW-UHFFFAOYSA-N 5-chloro-2h-benzotriazole Chemical compound C1=C(Cl)C=CC2=NNN=C21 PZBQVZFITSVHAW-UHFFFAOYSA-N 0.000 description 1
- CDTYDMKRNQVPFQ-UHFFFAOYSA-N 5-ethenyl-2h-benzotriazole Chemical compound C1=C(C=C)C=CC2=NNN=C21 CDTYDMKRNQVPFQ-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 208000002177 Cataract Diseases 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 208000010412 Glaucoma Diseases 0.000 description 1
- UXMQORVHJMUQFD-UHFFFAOYSA-N Heptanophenone Chemical compound CCCCCCC(=O)C1=CC=CC=C1 UXMQORVHJMUQFD-UHFFFAOYSA-N 0.000 description 1
- 235000015511 Liquidambar orientalis Nutrition 0.000 description 1
- HLJYBXJFKDDIBI-UHFFFAOYSA-N O=[PH2]C(=O)C1=CC=CC=C1 Chemical compound O=[PH2]C(=O)C1=CC=CC=C1 HLJYBXJFKDDIBI-UHFFFAOYSA-N 0.000 description 1
- OOPYUNNXQSWBQE-UHFFFAOYSA-N OC(C(=O)OC1=C(C(=O)C2=CC=CC=C2)C=CC(=C1)C)=C Chemical compound OC(C(=O)OC1=C(C(=O)C2=CC=CC=C2)C=CC(=C1)C)=C OOPYUNNXQSWBQE-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000004870 Styrax Substances 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- CKIDCRFWPRVLEU-UHFFFAOYSA-N [3-(benzotriazol-2-yl)-4-hydroxyphenyl] prop-2-enoate Chemical compound OC1=CC=C(OC(=O)C=C)C=C1N1N=C2C=CC=CC2=N1 CKIDCRFWPRVLEU-UHFFFAOYSA-N 0.000 description 1
- RKFUZDIZLQCJKA-UHFFFAOYSA-N [dimethyl(phenyl)silyl]methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC[Si](C)(C)C1=CC=CC=C1 RKFUZDIZLQCJKA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- WBLIXGSTEMXDSM-UHFFFAOYSA-N chloromethane Chemical compound Cl[CH2] WBLIXGSTEMXDSM-UHFFFAOYSA-N 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IQIJRJNHZYUQSD-UHFFFAOYSA-N ethenyl(phenyl)diazene Chemical compound C=CN=NC1=CC=CC=C1 IQIJRJNHZYUQSD-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000001595 flow curve Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002433 hydrophilic molecules Chemical class 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- RXRHXOLQBOFMDI-UHFFFAOYSA-N methoxymethane;2-methylprop-2-enoic acid Chemical compound COC.CC(=C)C(O)=O RXRHXOLQBOFMDI-UHFFFAOYSA-N 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VYQNWZOUAUKGHI-UHFFFAOYSA-N monobenzone Chemical compound C1=CC(O)=CC=C1OCC1=CC=CC=C1 VYQNWZOUAUKGHI-UHFFFAOYSA-N 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- YQCFXPARMSSRRK-UHFFFAOYSA-N n-[6-(prop-2-enoylamino)hexyl]prop-2-enamide Chemical compound C=CC(=O)NCCCCCCNC(=O)C=C YQCFXPARMSSRRK-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004978 peroxycarbonates Chemical class 0.000 description 1
- MDHYEMXUFSJLGV-UHFFFAOYSA-N phenethyl acetate Chemical compound CC(=O)OCCC1=CC=CC=C1 MDHYEMXUFSJLGV-UHFFFAOYSA-N 0.000 description 1
- FZGSCNQUWMMDIG-UHFFFAOYSA-N phenyl(phosphanyl)methanone Chemical compound PC(=O)C1=CC=CC=C1 FZGSCNQUWMMDIG-UHFFFAOYSA-N 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000036316 preload Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- NFRBUOMQJKUACC-UHFFFAOYSA-N triethyl(pentyl)azanium Chemical compound CCCCC[N+](CC)(CC)CC NFRBUOMQJKUACC-UHFFFAOYSA-N 0.000 description 1
- IXSPLXSQNNZJJU-UHFFFAOYSA-N trimethyl(silyloxy)silane Chemical compound C[Si](C)(C)O[SiH3] IXSPLXSQNNZJJU-UHFFFAOYSA-N 0.000 description 1
- QNWOFLWXQGHSRH-UHFFFAOYSA-N trimethyl-[methyl(trimethylsilyloxy)silyl]oxysilane Chemical class C[Si](C)(C)O[SiH](C)O[Si](C)(C)C QNWOFLWXQGHSRH-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/302—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and two or more oxygen atoms in the alcohol moiety
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/14—Eye parts, e.g. lenses or corneal implants; Artificial eyes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/14—Eye parts, e.g. lenses or corneal implants; Artificial eyes
- A61F2/16—Intraocular lenses
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/18—Internal ear or nose parts, e.g. ear-drums
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/16—Materials or treatment for tissue regeneration for reconstruction of eye parts, e.g. intraocular lens, cornea
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
- C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dermatology (AREA)
- General Health & Medical Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Veterinary Medicine (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Materials For Medical Uses (AREA)
- Prostheses (AREA)
Abstract
High refractive index acrylic acid device material is disclosed herein, there is the reflective of reduction.These device materials are particularly suited for use as ophthalmology or otorhinolaryngologicdevice device materials and including the monomers containing poly- (phenyl ether) and/or containing the crosslinking agent of poly- (phenyl ether).
Description
The present invention relates to ophthalmics and ear-nose-throat department device material.Specifically, the present invention relates to refer to high refractive power
Several and minimum reflective or not reflective soft acrylic material, these materials are particularly suitable for manufacture of intraocular crystalline lens (IOL).
Background of invention
As the recent technology development of micro-incision cataract operation and progress, increased emphasis have been placed into exploitation and are suitable for
On soft foldable materials in intraocular lens, being delivered by being less than the notch of 2.0mm.
A kind of currently known soft foldable material suitable for intraocular lens is soft hydrophobic acrylic materials, example
Such as U.S. Patent number 4834750,5,290,892,5,331,073,5,693,095,5,922,821,6241766,
6245106、6313187、6,353,069、6528602、6653422、6703466、6780899、6806337、6872793、
7585900、7652076、7714039、7790824、7790825、7799845、7847046、8058323、8,362,177、8,
8,449,610,8,557,892 466,209, described in (being combined in its entirety herein by reference herein) those.Those reports
The acryhic material in road usually has machinery and physical characteristic suitable for foldable intraocular lens (for example, below about 37 DEG C
Glass transition temperature, the Young's modulus less than 60Mpa, relatively high elongation at break, low viscosity greater than 100% etc.).
But they usually have the refraction index for higher than 1.50 but being lower than 1.56.In this way, those known acryhic materials can have
There are the restricted usages as micro-incision intraocular lens, since it is desired that thicker lenses realize given refractive power.
However, the increase of the refraction index with soft hydrophobic acrylic materials, reflective (or microvesicle) can be by this
It is become readily apparent from IOL made of material.It is reflective be present in the pettiness of the water of Medium Culture of IOL material to be mingled with, and by
It is visible in the difference of the refractive index between the water in IOL material and IOL material.It is reported that the poly- second two of dimethacrylate
Alcohol (PEG) ester and/or mono- (methyl) acrylic acid PEG ester can be used for improving the anti-reflective photosensitiveness of hydrophobic acrylic preparation.Referring to
For example, U.S. Patent number 5,693,095,6,353,069 and 8,449,610.But in order to minimize it to acryhic material
Refraction index ill-effect, it usually needs a small amount of dimethacrylate PEG ester or mono- (methyl) acrylic acid PEG ester are dense
Contracting object.Addition dimethacrylate PEG ester or mono- (methyl) acrylic acid PEG ester also tend to reduce the modulus of gained copolymer
And tensile strength.
Therefore, for its refraction index be higher than known acryhic material, have anti-reflective photosensitiveness and be suitable for manufacturer
The soft hydrophobic acrylic materials of the lenticular physics of work and mechanical property, which exist, to be needed.
Summary of the invention
In completing foregoing teachings, present disclosure simultaneously provides soft folding hydrophobic acrylic device material,
It is particularly suited for use as IOL, but it also acts as other ophthalmology or otorhinolaryngologicdevice device, such as contact lenses, artificial cornea, cornea
Ring or inlay, otology snorkel and rhinology implant.These polymer materials include the component containing poly- (phenyl ether).
Other than other factors, the present invention is partly based on the discovery that the monomer containing poly- (phenyl ether) can be used for
Manufacturing has from 1.57 to the soft hydrophobic acrylic device material of the refraction index higher than 1.58, which is higher than current
Those of known acryhic material.The present invention is also partly based on the discovery that by matching in acrylic artificial crystalline lens
The reactive straight chain polyalkylene glycol monomer of monomer and certain molecular weight containing poly- (phenyl ether) is applied in combination in product, hydrophobic third
Temperature-induced reflective formation can be efficiently reduced or eliminated in olefin(e) acid copolymer.Motif material is suitable for manufacture anti-reflective light
, low equilibrium moisture content, more high refractive index IOL.
Detailed description of the invention
Unless otherwise defined, all technical and scientific terms as used herein arrived have with it is of the art general
The logical normally understood identical meanings of technical staff.In general, nomenclature as used herein and laboratory procedure are well known and logical
It is usually used in this field.Conventional method is for those of offer in these programs, such as this field and various general referencess.
If term is provided with odd number, present invention also contemplates that the plural number of the term.Nomenclature as used herein and reality described below
It is well known in the art and those of common for testing room program.
As used herein " about " meaning be known as number " about " include described number plus or minus that
The 1%-10% of the number described.
" optional " or " optionally " mean that the event then described or situation may occur or may not occur, specification
Include the case where the event or happen and it not there is a situation where.
Unless otherwise noted, all components amount is presented based on % (w/w) (" weight % ").
Term " alkyl " refers to the monoradical obtained and removing hydrogen atom from straight chain or branch's alkane compound.Alkane
Another group in base (group) and organic compound forms key.
Term " alkylidene bivalent group " or " alkylidene diradical " or " alkyl diradical " interchangeably refer to logical
Cross the bivalent group for removing a hydrogen atom from alkyl and obtaining.Other groups in alkylidene bivalent group and organic compound
Form two keys.
Term " alkoxy (alkoxy or alkoxyl) " refers to by removing from the hydroxyl group of straight chain or branched alkyl groups alcohol
Hydrogen atom and the monoradical obtained.Another group in alkoxy (group) and organic compound forms key.
In this application, the term " substitution " about alkyl diradical or alkyl group mean the alkyl diradical or
The alkyl group includes at least one substituent group, which substitutes the alkyl diradical or the alkyl group
One hydrogen atom, and be to be selected from the group consisting of: hydroxyl (- OH), carboxyl (- COOH) ,-NH2, sulfydryl
(-SH)、C1-C4Alkyl, C1-C4Alkoxy, C1-C4Alkylthio group (alkyl sulfur compounds), C1-C4Acyl amino, C1-C4Alkyl amino,
Two-C1-C4Alkyl amino, halogen atom (Br or Cl), and combinations thereof.
In general, the present invention is for the ophthalmology or otorhinolaryngologicdevice device materials as soft hydrophobic acrylic materials.The present invention
Polymerism ophthalmology or otorhinolaryngologicdevice device materials have at 589nm and room temperature (23 DEG C ± 3 DEG C) fully hydrated state measure
1.57 or bigger (preferably 1.58 or bigger) refraction index, about 60MPa or smaller (preferably from about 1MPa to about 45MPa, more
Preferably from about 2.5MPa to about 30MPa, even more preferably from about 5MPa to the Young's modulus of 25MPa), about 35 DEG C or lower (excellent
Choosing about 30 DEG C or lower, more preferably from about -25 DEG C to 25 DEG C) glass transition temperature, at least 100% (preferably at least
110%, more preferably at least 120%, even more desirably at least 130%, most preferably from 130% to 300%) elongation, and
Obtained from include with formula (IA) containing poly- (phenyl ether) monomer and/or with formula (IB) containing poly- (phenyl ether) crosslinking agent can
Polymeric compositions
Wherein:
R1And R1' it is H or CH independently of one another3；
Ra、Rb、Rc、Rd、Re、Rf、Rg、Rh、Ri、Rj、Rk、Rl、Rm、Rn、Ro、RpAnd RqIt is H, C independently of one another1-C12Alkane
Base or C1-C12Alkoxy (being preferably entirely H)；
B1And B1' it is direct key, (CH independently of one another2)m1Or (OCH2CH2)m2, wherein m1 is 2-6 and m2 is 1-10；
Q1And Q1' it is direct key, O, NH or C (=O) NH (CH independently of one another2)m3O, wherein m3 is the integer of 2-6；
N1 is from 1 to 9 (preferably from 2 to 6, more preferably from 2 to 4, even more preferably 2 or integer 3)；
N2 and n2 ' is the integer of from 0 to 6 (preferably from 0 to 4) independently of one another；
N3 is the integer of from 1 to 100 (preferably from 5 to 75, more preferably from 20 to 60)；And
Y1And Y1' it is direct key, O, S, OC (=O) NH, NHC (=O) NH or NR ' independently of one another, wherein R ' is H, C1-
C10Alkyl, C6H5Or CH2C6H5。
In order in IOL, device material of the invention should not have a glass transition temperature (Tg) higher than 37 DEG C, and 37
It DEG C is normal human body temperature.Material with the glass transition temperature higher than 37 DEG C is not suitable for making in foldable IOL
With；Such lens only can be rolled or be folded being higher than 37 DEG C, and will not be unfolded at normal body temperature or unfolding.The present invention
Ophthalmic device material preferably there are about 30 DEG C or lower, more preferably from about -25 DEG C to 25 DEG C of glass transition temperature, thus
The material is allowed advantageously to roll or fold at room temperature.Tg is to be measured by differential scanning calorimetry with 10 DEG C/min,
And it is measured at the midpoint of heat flow curve transformation.
For in IOL, device material preferred display of the invention goes out enough intensity to allow to be made of them
Device fold or operate without rupture.Therefore, ophthalmic device material of the invention will have at least 100%, preferably at least
130% and the elongation (% breaking strain) most preferably between 130% and 300%.The characteristic is indicated by this material system
At lens fold when usually will not rupture, tear or crack.The elongation of polymer samples is in dumb-bell shape extension test sample
It is measured on product, the total length of the test sample is 20mm, and the length of clamp area is 4.88mm, overall width 2.49mm, narrow
Partial width is 0.833mm, and radius of corner is 8.83mm and with a thickness of 0.9mm.At ambient conditions (23 DEG C ± 2 DEG C, 50%
± 5% relative humidity) use Instron material testing machine (the Instron Material with 50 Newton Load Cells
Tester) (No.4442 type or equivalent) is tested on sample.Clamp distance is set as 14mm, and by crosshead
Speed is set as 500mm/ minutes, and sample is stretched until destroying.Elongation (strain) is reported as destroying
When score of the displacement relative to original grip distance.Breaking strain is reported as displacement when destroying relative to original grip distance
Score.Fracture strength calculates under the peak load of sample, load when typically sample is broken, wherein it is assumed that primary face
Product is kept constant.Young's modulus is calculated by the instantaneous slope of load-deformation curve in linear elasticity area.By 25% secant modulus meter
Calculate the slope of the straight line to draw between the strain of load-deformation curve 0% and 25% strain.100% secant modulus is calculated
Slope for the straight line drawn between the strain of load-deformation curve 0% and 100% strain.Due on material to be tested
For mollielast, they are loaded into Instron machine and is tended to so that they are deformed.In order to remove the pine in material sample
It relaxes, is placed in preloading on sample.This helps to reduce relaxation and provides more consistent reading.When by sample preload extremely
(when typically 0.03 to 0.05N), strain is set as 0 to desirable value, and starts to test.
IOL is applied, the rigidity of device material must be sufficiently low to allow to fold and (such as the 1- that is open by minor diameter
3mm) injection is without tearing after the implantation or deforming.In a preferred embodiment, the Young's modulus of the device material will be about
60Mpa or smaller (preferably from about 1MPa to about 45Mpa, more preferably from about 2.5MPa to about 30Mpa, even more preferably from about
5MPa to 25MPa.
Device material of the invention preferably further have across 16 DEG C of -45 DEG C of temperature ranges (preferably less than 2.0 weight %
About 1.6% or smaller, more preferably from about 1.2% or smaller, even more preferably about 1.0% or smaller) equilibrium moisture content, and it is excellent
Selection of land is in 16 DEG C of -23 DEG C of temperature ranges less than the equilibrium moisture content of 2.5 weight %.These device materials are preferably anti-reflective light
, so that should be generated very as little as when being balanced in water at 45 DEG C and then allowing for being cooled to environment temperature (about 22 DEG C)
Microvesicle is not generated, as detected by microexamination.
Poly- (phenyl ether) monomer that contains with formula (IA) can be from simple function polyphenyl ether (that is, having a functional group such as
Those of hydroxyl, amino or carboxylic group) preparation.In general, under the conditions of coupling reaction well known by persons skilled in the art, it is single
Function, OH- sealing end poly- (phenyl ether) and (methyl) acrylic acid derivative (such as acryloyl chloride, methacrylic chloride, methyl
Acrylic anhydride or acrylic acid isocyanide acyl alkyl ester or methacrylic acid isocyanide acyl alkyl ester) reaction.Use suitable (methyl) propylene
Acid derivative, the polyphenyl ether blocked in a similar manner to monoamine and monocarboxylic acid are functionalized.The polyphenyl of the sealing end of simple function
Base ether can according in document (Journal of Organic Chemistry (J.Org.Chem.), 1960,25 (9), the 1590-1595 pages, by drawing
With combining in its entirety herein) it is prepared by the program of description.
The crosslinking agent containing poly- (phenyl ether) with formula (IB) can from difunctionality sealing end polyphenyl ether (that is, having
Two functional end-groups such as those of hydroxyl, amino or carboxylic group) preparation.In general, well known by persons skilled in the art
Under reaction condition, bifunctional, OH- sealing end poly- (phenyl ether) and (methyl) acrylic acid derivative (such as acryloyl chloride, methyl
Acryloyl chloride, methacrylic anhydride or acrylic acid isocyanide acyl alkyl ester or methacrylic acid isocyanide acyl alkyl ester) reaction.Using suitable
(methyl) acrylic acid derivative closed, in a similar manner to difunctionality, amine-and carboxylic acid-sealing end polyphenyl ether carry out function
Change.The polyphenyl ether of the sealing end of difunctionality can be according in United States Patent (USP) 5021543 (being combined herein) in its entirety by quoting
It is prepared by the program of description.
In a preferred embodiment, the monomer containing poly- (phenyl ether) in polymerisable compound is indicated by formula (IA), wherein
N1 is 2 or 3.The example of such preferably monomer containing poly- (phenyl ether) includes but not limited to:
In a preferred embodiment, the polymerisable compound of ophthalmic device material for manufacturing the present invention includes: a) by weight
Meter is from about 40% to about 95% (preferably by weight from about 45% to about 85%, more preferably by weight from about 50% to about
75%) monomer and b containing poly- (phenyl ether) of at least one with formula as defined above (IA)) by weight from about 1%
To the polymerizable components containing poly(ethylene glycol) of about 6% (preferably by weight from about 2% to about 5%), the polymerizable components packet
Containing at least one polymerizable groups, which is acryloyl group (OC (=O) CH ═ CH2), metering system
Acyl group (OC (=O) CCH3═CH2), acrylamido (NHC (=O) CH ═ CH2), methacryl amido (NHC (=O) CCH3
═CH2) or mercapto, preferably acryloyl group, methylacryloyl, acrylamido or methacryl amido group,
More preferably acryloyl group or methylacryloyl, even more preferably acryl group.It should be understood that weight percent is base
The total amount of polymerizable components in polymerisable compound.
According to the present invention, the polymerizable components containing poly(ethylene glycol) can be with one or two end as described above
The straight chain poly(ethylene glycol) of polymerizable groups, or the branch with three or more terminal polymerizable groups as described above are poly-
(ethylene glycol).This polymerizable components containing poly(ethylene glycol) can have from commercially available according to procedures known in the art
It is prepared by the polyethylene glycol of one or more functional end-groups (such as hydroxyl, amino or carboxylic group).In general, have one or
The poly(ethylene glycol) of multiple hydroxyl terminal groups is dissolved in tetrahydrofuran, and (first is used in the presence of triethylamine or pyridine
Base) acrylic acid derivative such as methacrylic chloride or methacrylic anhydride handled.The reaction carries out the hydroxyl until 90%
Base group has been converted into corresponding acrylate or methacrylate.The polymer solution is filtered, and should
Polymer is separated and being deposited in diethyl ether.Using suitable (methyl) acrylic acid derivative, in a similar way, by amine
It is functionalized with carboxylic acid-terminated polyethylene glycol.
Preferably, the polymerizable components containing poly(ethylene glycol) used in the present invention are indicated by formula (II)
Wherein: A ' is H or CH3；
Q and Q' is direct key, O, NH or C (=O) NHCH independently of one another2CH2O；
X and X ' is independently direct key, O, NH, OC (=O) NH or NHC (=O) NH；
R and R' is direct key or (CH independently of one another2)p；
P=1-3；
M=2-6；
G is H, C1-C4Alkyl, (CH2)mNH2、(CH2)mCO2Or R'-X'-Q'-C (=O) CA' ═ CH H,2；And
As G=H, C1-C4Alkyl, (CH2)mNH2Or (CH2)mCO2When H, n=45-225；Otherwise n=51-225.
The polymerizable components containing poly(ethylene glycol) with formula (II) can be manufactured by method as known in the art.Example
It such as, can be according to above procedure or as described in U.S. Patent number 8,449,610 (being combined in its entirety herein by quoting)
Prepare them.
The preferred polymerizable components containing poly(ethylene glycol) with formula (II) are with those of following situations: wherein: X
It is direct key or O independently of one another with X'；R and R ' is direct key；Q and Q' is direct key or C (=O) independently of one another
NHCH2CH2O；A ' is H or CH3；G is C1-C4Alkyl or R'--X'-Q'--C (=O) CA ' ═ CH2；And work as G=C1-C4Alkyl
When n=45-180；Otherwise n=51-225.
Although the total amount for the component with formula (II) for including in device material of the invention is relative to device material
It is 1%-5% by weight for the total amount of polymerizable components, is preferably 2%-5% by weight, and most preferably by weight
Meter is 2%-4%, this amount may include having the combination of a kind of component or the various ingredients with formula (II) of formula (II).Tool
Having the component of formula (II) has 2,000-10,000 dalton, preferably 2,000-8,000 dalton, more preferable 2,000-6,000
The number-average molecular weight of dalton and most preferably 2,500-6,000 dalton.
In a further advantageous embodiment, the polymerisable compound of this ophthalmic device material for manufacturing the present invention into
One step include by weight from about 10% to about 45% (preferably by weight from about 15% to about 40%, more preferably by weight
There are the aryl acrylic monomers of formula (III) from about 20% to one or more about 35%)
Wherein: A is H or CH3；
B2It is (CH2)mOr [O (CH2)2]Z；
M is 2-6；
Z is 1-10；
Y is direct key, O, S or NR', and condition is if Y is O, S or NR', and B is (CH2)m；
R' is H, CH3、Cn'H2n'+1, iso- OC3H7、C6H5Or CH2C6H5；
N '=1-10；
W is 0-6, and condition is m+w≤8；And
D is H, Cl, Br, C1-C4Alkyl, C1-C4Alkoxy, C6H5Or CH2C6H5。
Monomer with formula (III) can be manufactured by method as known in the art.For example, being total to for required monomer can be made
Yoke alcohol is combined with methyl acrylate, butyl titanate (catalyst) and polymerization initiator such as 4- benzyloxy phenol in reaction vessel
In.Then container is heated to promote to react and distill byproduct of reaction to drive reaction to be completed.Alternative synthetic schemes
It is related to for acrylic acid being added in conjugated alcohol and with carbodiimide catalyzed or by conjugated alcohol and acryloyl chloride and alkali (such as pyridine or three second
Amine) mixing.
The suitable monomer with formula (III) includes but is not limited to: acrylic acid 2- ethyl phenoxy group ester；Methacrylic acid 2-
Ethyl phenoxy group ester；Phenyl acrylate；Phenyl methacrylate；Benzyl acrylate；Benzyl methacrylate；Acrylic acid 2- phenyl
Ethyl ester；Methacrylic acid 2- phenyl chlorocarbonate；Acrylic acid 3- phenylpropyl acrylate；Methacrylic acid 3- phenylpropyl acrylate；Acrylic acid 4- phenyl
Butyl ester；Methacrylic acid 4- butyloxy phenyl；Acrylic acid 4- methyl phenyl ester；Methacrylic acid 4- methyl phenyl ester；Acrylic acid 4- methyl
Benzyl ester；Methacrylic acid 4- methyl benzyl ester；Acrylic acid 2,2- aminomethyl phenyl ethyl ester；Methacrylic acid 2,2- aminomethyl phenyl ethyl ester；
Acrylic acid 2,3- aminomethyl phenyl ethyl ester；Methacrylic acid 2,3- aminomethyl phenyl ethyl ester；Acrylic acid 2,4- aminomethyl phenyl ethyl ester；Methyl
Acrylic acid 2,4- aminomethyl phenyl ethyl ester；Acrylic acid 2- (4- propyl phenyl) ethyl ester；Methacrylic acid 2- (4- propyl phenyl) ethyl ester；
Acrylic acid 2- (4- (1- Methylethyl) phenyl) ethyl ester；Methacrylic acid 2- (4- (1- Methylethyl) phenyl) ethyl ester；Acrylic acid
2- (4- methoxyphenyl) ethyl ester；Methacrylic acid 2- (4- methoxyphenyl) ethyl ester；Acrylic acid 2- (4- cyclohexyl phenyl) second
Ester；Methacrylic acid 2- (4- cyclohexyl phenyl) ethyl ester；Acrylic acid 2- (2- chlorphenyl) ethyl ester；Methacrylic acid 2- (2- chlorobenzene
Base) ethyl ester；Acrylic acid 2- (3- chlorphenyl) ethyl ester；Methacrylic acid 2- (3- chlorphenyl) ethyl ester；Acrylic acid 2- (4- chlorphenyl)
Ethyl ester；Methacrylic acid 2- (4- chlorphenyl) ethyl ester；Acrylic acid 2- (4- bromophenyl) ethyl ester；Methacrylic acid 2- (4- bromophenyl)
Ethyl ester；Acrylic acid 2- (3- phenyl) ethyl ester；Methacrylic acid 2- (3- phenyl) ethyl ester；Acrylic acid 2- (4- phenyl benzene
Base) ethyl ester；Methacrylic acid 2- (4- phenyl) ethyl ester；Acrylic acid 2- (4- benzyl phenyl) ethyl ester；Methacrylic acid 2- (4-
Benzyl phenyl) ethyl ester；Acrylic acid 2- (thiophenyl) ethyl ester；Methacrylic acid 2- (thiophenyl) ethyl ester；Acrylic acid 2- benzyloxy second
Ester；Acrylic acid 3- benzyloxy propyl ester；Methacrylic acid 2- benzyloxy ethyl ester；Methacrylic acid 3- benzyloxy propyl ester；Acrylic acid 2-
[2- (benzyloxy) ethyoxyl] ethyl ester；Methacrylic acid 2- [2- (benzyloxy) ethyoxyl] ethyl ester；Or combinations thereof.
The preferred aryl acrylic monomers with formula (I) are the wherein B with those of following situations1It is (CH2)m1, m1
It is 2-5, Y1Be without or O, w1 be 0 or 1, and D1It is H.Most preferably acrylic acid 2- phenyl chlorocarbonate；Acrylic acid 3- phenyl third
Ester；Acrylic acid 4- butyloxy phenyl；Acrylic acid 5- phenylpentyl；Acrylic acid 2- benzyloxy ethyl ester；Acrylic acid 3- benzyloxy propyl ester；Third
Olefin(e) acid 2- [2- (benzyloxy) ethyoxyl] ethyl ester；And their corresponding methacrylate.
The polymerisable compound of this ophthalmic device material for manufacturing the present invention preferably further includes polymerizable
Crosslinking agent.Crosslinking agent can be any terminal ethylene formula unsaturated compound with more than one unsaturated group.Suitable
Crosslinking agent includes for example: ethylene glycol dimethacrylate；Diethyleneglycol dimethacrylate；Three second two of dimethacrylate
Alcohol ester, dimethacrylate tetraethylene glycol ester, allyl methacrylate；Dimethacrylate 1,3- propylene glycol ester；Diformazan
Base acrylic acid 2,3- propylene glycol ester；Dimethacrylate 1,6-HD ester；Dimethacrylate 1,4- butanediol ester；Two propylene
Sour glycol ester；Diethyleneglycol diacrylate；Diacrylate triglycol ester, diacrylate tetraethylene glycol ester, acrylic acid alkene
Propyl diester；Diacrylate 1,3- propylene glycol ester；Diacrylate 2,3- propylene glycol ester；Diacrylate 1,6-HD ester；Two propylene
Sour 1,4- butanediol ester；N, N '-hexa-methylene bisacrylamide；N, N '-hexamethylene bis Methacrylamide；N, N '-dihydroxy
Base ethylenebisacrylamide；The double Methacrylamides of N, N '-dihydroxy ethylidene；N, N '-methylene-bisacrylamide；N,
N '-methylenebismethacrylamide；CH2=C (CH3) C (=O) O- (CH2CH2O)p- C (=O) C (CH3)=CH2, wherein p=
1-50；CH2=CHC (=O) O- (CH2CH2O)p- C (=O) CH=CH2, wherein p=1-50；CH2=C (CH3) C (=O) O
(CH2)tO-C (=O) C (CH3)=CH2, wherein t=3-20；And CH2=CHC (=O) O (CH2)tO-C (=O) CH=CH2,
Middle t=3-20.Preferred cross-linking monomer is CH2=C (CH3) C (=O) O- (CH2CH2O)p- C (=O) C- (CH3)=CH2, wherein
P makes number average molecular weight be about 400, about 600 or about 1000.Other preferred cross-linking monomers are ethylene glycol dimethacrylate
Ester (EGDMA), diethyleneglycol dimethacrylate, diethylene glycol dimethacrylate, diacrylate triglycol ester, with
And diacrylate 1,4- butanediol ester (BDDA).
In general, the total amount of cross-linking component is by weight depending on the characteristic and concentration of remaining component and required physical characteristic
Meter at least 0.1%, range is up to by weight about 20%.The preferred concentration range of the cross-linking component is: typical for having
Less than being 1%-5% for the small hydrophobic compound of the molecular weight of 500 dalton, and for bigger hydrophilic compounds
For 5%-17% (w/w).
In addition to one or more monomers with formula (I), one or more monomers with formula (II), one or more tools
Have except the monomer and one or more crosslinking agents of formula (III), ophthalmic device material of the invention can also include other at
Point, including but not limited to: polymerizable UV- absorbent (or UV- absorption reagent), polymerizable colored dyes, viscous to reduce
The additive of property, siloxanyl monomers, and combinations thereof.
Polymerizable ultraviolet (UV) absorbent can also reside in material of the invention.Polymerizable UV absorbent can be
It absorbs UV light (that is, light with the shorter than wavelength of about 380nm) and optionally absorbs high energy purple light (HEVL) (that is, having
The light of wavelength between 380nm and 440nm) but the visible light wavelength of 440nm (have greater than) of any significant quantity is not absorbed
Any compound.UV absorbing compounds are incorporated in monomer mixture and are captured on polymer in monomer mixture polymerization
In matrix.Any suitable polymerizable UV absorbent can be used in the present invention.What is be used in the present invention is polymerizable
UV absorbent includes benzophenone part or preferred benzotriazole part.UV absorbent containing polymerisable benzophenone can basis
U.S. Patent number 3,162,676 and 4,304,895 (combines herein) described program preparation in its entirety by quoting or can be from
Commercial supplier obtains.UV absorbent containing polymerizable benzotriazole can according to U.S. Patent number 3,299,173,4,612,
358,4,716,234,4,528,311,8,153,703 and US 8,232,326 (being combined in its entirety herein by quoting)
Described program is prepared or can be obtained from commercial supplier.
Preferably the example of the UV absorbent containing polymerisable benzophenone includes but not limited to: 2- hydroxyl -4- acryloyl
Oxygroup alkoxy benzophenone, 2- hydroxy-4-methyl acryloxy alkoxy benzophenone, allyl -2- hydroxy benzophenone
Ketone, 4- acryloyl group ethyoxyl -2- dihydroxy benaophenonel (UV2), 2- hydroxy-4-methyl acryloxybenzophenone (UV7),
Or combinations thereof.
Preferably the example of the UV- absorbent containing polymerizable benzotriazole and UV/HEVL absorbent includes but not limited to:
2- (2- hydroxyl -5- ethenylphenyl) -2H- benzotriazole, 2- (2- hydroxyl -5- acryloxy phenyl) -2H- benzotriazole,
2- (2- hydroxy-3-methyl acryloyl group amide methyl -5- t-octyl phenyl) benzotriazole, 2- (2'- hydroxyl -5'- methyl-prop
Enoyl- amidophenyl) -5- chlorobenzotriazole, 2- (2'- hydroxyl -5'- methacryl amide base phenyl) -5- methoxyl group
Benzotriazole, 2- (2'- hydroxyl -5'- methacryloxypropyl -3'- tbutyl-phenyl) -5- chlorobenzotriazole, 2- (2'-
Hydroxyl -5'- methacryloxypropyl phenyl) benzotriazole, methacrylic acid 2- hydroxy-5-methyl oxygroup -3- (5- (trifluoro
Methyl) -2H- benzo [d] [1,2,3] triazole -2- base) benzyl ester (WL-1), methacrylic acid 2- hydroxy-5-methyl oxygroup -3- (5- first
Oxygroup -2H- benzo [d] [1,2,3] triazole -2- base) benzyl ester (WL-5), methacrylic acid 3- (the fluoro- 2H- benzo [d] of 5- [1,2,
3] triazole -2- base) -2- hydroxy-5-methyl oxygroup benzyl ester (WL-2), methacrylic acid 3- (2H- benzo [d] [1,2,3] triazole -2-
Base) -2- hydroxy-5-methyl oxygroup benzyl ester (WL-3), methacrylic acid 3- (chloro- 2H- benzo [d] [1,2,3] triazole -2- base of 5-) -
2- hydroxy-5-methyl oxygroup benzyl ester (WL-4), methacrylic acid 2- hydroxy-5-methyl oxygroup -3- (5- methyl -2H- benzo [d] [1,2,
3] triazole -2- base) benzyl ester (WL-6), methacrylic acid 2- hydroxy-5-methyl base -3- (5- (trifluoromethyl) -2H- benzo [d] [1,
2,3] triazole -2- base) benzyl ester (WL-7), 4- allyl -2- (chloro- 2H- benzo [d] [1,2,3] triazole -2- base of 5-) -6- methoxy
Base phenol (WL-8), 2- { 2 '-hydroxyls -3 '-tert- 5 ' [3 "-(4 "-vinyl benzyl oxygroup) propoxyl group] phenyl } -5- methoxyl group -
2H- benzotriazole, phenol, 2- (the chloro- 2H- benzotriazole -2- base of 5-) -6- (1,1- dimethyl ethyl) -4- vinyl -
(UVAM), 2- (2'- hydroxyl -5'- methaciylyloxyethylphenyl) benzotriazole (2- acrylic acid, 2- methyl -, 2- [3-
(2H- benzotriazole -2- base) -4- hydroxy phenyl] ethyl ester, Norbloc), 2- { 2 '-hydroxyls -3 '-tert-butyl -5 '-[3 '-methyl
Acryloxy propoxyl group] phenyl } -5- methoxyl group -2H- benzotriazole (UV13), 2- [2 '-hydroxyls -3 '-tert-butyl -5 ' -
(3 '-acryloxy propoxyl group) phenyl] -5- trifluoromethyl -2H- benzotriazole (CF3- UV13), 2- (2 '-hydroxy-5-methyl bases
Acryloyl group amidophenyl) -5- methoxyl group benzotriazole (UV6), 2- (3- allyl -2- hydroxy-5-methyl base phenyl) -2H-
Benzotriazole (UV9), 2- (2- hydroxyl -3- methylallyl -5- aminomethyl phenyl) -2H- benzotriazole (UV12), the tertiary fourth of 2-3 ' -
Base -2 '-hydroxyl -5 '-(3 "-dimethylvinylsilyl propoxyl group) -2 '-hydroxy-phenies) -5- methoxyl group benzotriazole
(UV15), 2- (2 '-hydroxyls -5 '-methyclyloxypropyl -3 '-tbutyl-phenyl) -5- methoxyl group -2H- benzotriazole
(UV16), 2- (2 '-hydroxyls -5 '-acryloyl propyl group -3 '-tbutyl-phenyl) -5- methoxyl group -2H- benzotriazole
(UV16A), 2- methacrylic acid 3- [3- tert-butyl -5- (5- chlorobenzotriazole -2- base) -4- hydroxy phenyl]-propyl ester (16-
100, CAS#96478-15-8), methacrylic acid 2- (3- (tert-butyl) -4- hydroxyl -5- (5- methoxyl group -2H- benzo [d] [1,
2,3] triazole -2- base) phenoxy group) ethyl ester (16-102)；Phenol, 2- (the chloro- 2H- benzotriazole -2- base of 5-) -6- methoxyl group -4-
(2- propylene -1- base) (CAS#1260141-20-5)；2- [2- hydroxyl -5- [3- (methacryloxy) propyl] -3- tert-butyl
Phenyl] the chloro- 2H- benzotriazole of -5-；Phenol, 2- (5- vinyl -2H- benzotriazole -2- base) -4- methyl -, homopolymer (9CI)
(CAS#83063-87-0)。
It is highly preferred that polymerizable UV absorbent is 2- (2H- benzo [d] [1,2,3] triazole -2- base) -4- methyl -6-
(2- methacrylic) phenol (oNTP), methacrylic acid 3- [3- tertiary butyl-4-hydroxy -5- (5- methoxyl group -2- benzo [d]
[1,2,3] triazole -2- base) phenoxy group] propyl ester (UV13) and methacrylic acid 2- [3- (2H- benzotriazole -2- base) -4- hydroxyl
Base phenyl] ethyl ester (Norbloc 7966), or combinations thereof.
In addition to ultraviolet absorbability material, the ocular devices made of copolymer of the invention may include colored dyes, example
Weld as disclosed in U.S. Patent number 5,470,932.
Device material of the invention can also include the additive to reduce or remove viscosity.The example of such additives
Including those of being disclosed in U.S. Patent number 7,585,900 and 7,714,039, their full content is incorporated by reference
Herein.
In one embodiment, device material of the invention also letter of guarantee has the siloxanyl monomers of formula (IV)
Wherein
R2It is H or CH3；
T is direct key, O (CH2)bOr OCH2CH(OH)CH2；
B is 1-3；
J is (CH2)z；And
K1、K2And K3It is independently CH3、C6H5Or OSi (CH3)3。
Monomer with formula (IV) can be made up of known method, and be commercially available in some cases.It is excellent
The monomer with formula (IV) of choosing is the wherein R with those of following situations2It is CH3, T is direct key or OCH2CH(OH)CH2,
J is (CH2)3, and K1、K2And K3It is independently CH3、C6H5Or OSi (CH3)3。
Most preferred monomer with formula (IV) is those of to be selected from the group, the group consisting of: methacrylic acid
3- [three (trimethyl silyl oxygroup) silicyls]-propyl ester (" TRIS ")；3- (methacryloxy -2- the third oxygen of hydroxyl
Base) bis- (trimethoxy) silane (SiMA) of hydroxypropyl methyl；Methacryloxypropyl pentamethyl disiloxane；3- metering system
Bis- (trimethylsiloxy) methyl-monosilanes of acryloxypropylethoxysilane；Methacryloxymethyl three (trimethylsiloxy)
Silane；(methacryloxymethyl) phenyl-dimethyl silane；And (methacryloxymethyl) bis- (trimethyl first
Siloxy) methyl-monosilane.
The range of the amount of monomer in material of the invention with formula (IV) will be from 5%-30%, preferably 5%-
25%, and most preferably 5%-15%.
Copolymer of the invention is prepared by typical polymerization methods.For example, preparation has formula in desired ratio
(I)-(III) liquid monomer and crosslinking agent are together with any other polymerizable components such as UV absorbent, weld, and/or use
To drop the mixture of the thermal free radical initiator of less viscous additive and routine.Then the mixture can be introduced has
In the mold of desirable shape, and with hot (passing through heating) or photochemistry (i.e. by actinic radiation, for example, UV radiate and/or
Visible optical radiation) method polymerize to activate initiator.
The example of suitable thermal initiator includes but is not limited to: azonitrile, such as 2, bis- (2, the 4- dimethyl-pentens of 2'- azo
Nitrile), 2,2'- azo bis- (2- methyl propionitrile), 2,2'- azo bis- (2- methylbutyronitriles), 2,2 '-azos it is bis- (isobutyronitrile)
(AIBN)；Peroxide, such as benzoyl peroxide；Peroxy carbonates, such as double-(4- tert-butylcyclohexyl) peroxycarbonic acid hydrogen
Ester, and the like.Preferred initiator is AIBN.
When being polymerize by photochemical method, mold reply is in the actinic radiation with the wavelength that can cause polymerization
It is transparent.Can also introduce Conventional photoinitiators compound such as diphenyl ketone type or double acylphosphine oxides (BAPO) photoinitiator with
Promote polymerization.Suitable photoinitiator is styrax methyl ether, diethoxy acetophenone, benzoylphosphine oxide, 1- hydroxyl ring
(preferably up to promise is solid for hexyl phenyl ketone, Da Nuogu (Da Nuogu) and gorgeous good solid (Irgacur) type photoinitiatorDa Nuo is solidWith it is gorgeous good solid) and be based on germane (Germane) Norrish (Norrish) I type photoinitiator,
Free radical polymerization can be caused under the radiation of light source comprising the light in the range of about 400 to about 550nm.Benzoyl phosphine causes
The example of agent includes 2,4,6- trimethyl benzoyl diphenyl base phosphine oxide；Double-(2,6- dichloro-benzoyl base) -4-N- propylbenzene
Base phosphine oxide；And double-(2,6- dichloro-benzoyl base) -4-N- butyl phenyl phosphine oxide.Norrish's I type light based on germane draws
The example of hair agent is acyl group germanium compound described in US 7,605,190 (being combined in its entirety herein by quoting).
Regardless of selected initiator or curing method, curing method should be controlled to avoid rapid polymerization, this can be obtained
There is the polymeric material of more viscosity to the identical material than more slowly polymerizeing.
Once ophthalmic device material of the invention is cured, they are extracted in a suitable solvent to remove as much as possible
Go the unreacted components of material.The example of suitable solvent includes acetone, methanol and hexamethylene.The solvent for being preferably used in extraction is
Acetone.
Can have by the IOL that the ophthalmic device material disclosed is constituted any can be rolled into or be folded into small cross section
Design, which can fit through relatively small notch.It is set for example, IOL can be referred to as one integral piece designs or more than one piece
Meter.Typically, IOL includes visual component and at least one haptic.Visual component is the part as lens, tactile
Part is attached on visual component and is maintained at the suitable position in eye as arm by visual component.Visual component and one or
Multiple haptics can be identical or different material.Multi-piece type lens are so gained the name, be due to visual component and one or
Multiple haptics are separately fabricated, and then haptic is attached on visual component.In single-piece lens, visual component and
Haptic is formed by a material.Depending on material, then cutting or turning go out haptic to produce from the material
IOL。
In addition to IOL, ophthalmic device material of the invention is applied also in other devices, including contact lenses, artificial cornea,
Intracorneal lens, corneal inlay or ring and glaucoma filtration device.
These device materials can be used to form the intraocular lens with low surface viscosity and high refractive index.By these materials
Lens made of expecting be it is flexible and transparent, can be inserted into eye by lesser notch, and restore after insertion they just
Beginning shape.
Although having used specific term, Apparatus and method for, various embodiments of the present invention have been described, such description
It is for illustration purposes only.Used word is descriptively rather than restrictive word.It should be appreciated that can be by this field skill
Art personnel make change and variation under without departing from the spirit or scope of the present invention described in following claims.This
Outside, it should be appreciated that many aspects of each embodiment can be exchanged wholly or partly or can be combined in any manner
And/or be used together, it is as demonstrated below:
1. a kind of polymerism ophthalmology or otorhinolaryngologicdevice device materials have at 589nm and room temperature (23 DEG C ± 3 DEG C) complete
The refraction index of 1.57 or bigger (preferably 1.58 or bigger) of full hydrated state measurement, about 60MPa or smaller (preferably from about 1MPa
To about 45MPa, more preferably from about 2.5MPa to about 30MPa, even more preferably from about 5MPa to the Young's modulus of 25MPa), about 35
DEG C or lower (preferably from about 30 DEG C or lower, more preferably from about -25 DEG C to 25 DEG C) glass transition temperature, at least 100% is (excellent
Choosing at least 110%, more preferably at least 120%, even more desirably at least 130%, most preferably from 130% to 300%) elongation
Rate, wherein the polymerism ophthalmology or otorhinolaryngologicdevice device materials are the copolymerization product of polymerisable compound, the polymerisable compound
Including the monomer with formula (IA) containing poly- (phenyl ether) and/or with the crosslinking agent containing poly- (phenyl ether) of formula (IB)
Wherein:
R1And R1' it is H or CH independently of one another3；
Ra、Rb、Rc、Rd、Re、Rf、Rg、Rh、Ri、Rj、Rk、Rl、Rm、Rn、Ro、RpAnd RqIt is H, C independently of one another1-C12Alkane
Base or C1-C12Alkoxy (preferably H)；
B1And B1' it is direct key, (CH independently of one another2)m1Or (OCH2CH2)m2, wherein m1 is 2-6 and m2 is 1-10；
Q1And Q1' it is direct key, O, NH or C (=O) NH (CH independently of one another2)m3O, wherein m3 is the integer of 2-6；
N1 is from 1 to 9 (preferably from 2 to 6, more preferably from 2 to 4, even more preferably 2 or integer 3)；
N2 and n2 ' is the integer of from 0 to 6 (preferably from 0 to 4) independently of one another；
N3 is the integer of from 1 to 100 (preferably from 5 to 75, more preferably from 20 to 60)；And
Y1And Y1' it is direct key, O, S, OC (=O) NH, NHC (=O) NH or NR ' independently of one another, wherein R ' is H, C1-
C10Alkyl, C6H5Or CH2C6H5。
2. the device material as described in invention 1, wherein the polymerism ophthalmology or otorhinolaryngologicdevice device materials have in 589nm
With 1.58 or the bigger refraction index measured under room temperature (23 DEG C ± 3 DEG C) in fully hydrated state.
3. the device material as described in invention 1 or 2, wherein the polymerism ophthalmology or otorhinolaryngologicdevice device materials have from about
1MPa to about 45MPa (more preferably from about 2.5MPa to about 30Mpa, even more preferably from about 5MPa to the Young's modulus of 25MPa).
4. the device material as described in invention any one of 1 to 3, wherein the polymerism ophthalmology or otorhinolaryngologicdevice device materials
With about 30 DEG C or the glass transition temperature of lower (more preferably from about -25 DEG C to 25 DEG C), at least 100% (preferably at least
110%, more preferably at least 120%, even more desirably at least 130%, most preferably from 130% to 300%) elongation.
5. the device material as described in invention any one of 1 to 4, wherein the polymerism ophthalmology or otorhinolaryngologicdevice device materials
Elongation at least 110% (more preferably at least 120%, even more desirably at least 130%, most preferably from 130% to 300%)
Rate.
6. the device material as described in any one of invention 1 to 5, wherein in formula (IA) and (IB), Ra、Rb、Rc、Rd、Re、
Rf、Rg、Rh、Ri、Rj、Rk、Rl、Rm、Rn、Ro、RpAnd RqIt is H independently of one another.
7. the device material as described in any one of invention 1 to 6, wherein n1 is from 2 to 6 in formula (IA) and (IB)
Integer (more preferably from 2 to 4, even more preferably 2 or 3).
8. the device material as described in any one of invention 1 to 7, wherein n2 and n2 ' are only each other in formula (IA) and (IB)
It is on the spot from 0 to 4 integer.
9. the device material as described in any one of invention 1 to 8, wherein n3 is from 5 to 75 in formula (IA) and (IB)
The integer of (more preferably from 20 to 60).
10. the device material as described in invention any one of 1 to 9, wherein the polymerisable compound includes:
A) by weight from about 40% to about 95% (preferably by weight from about 45% to about 85%, more preferably by weight
It counts from about 50% monomer containing poly- (phenyl ether) to about 75%) at least one with formula as defined above (IA)；And
B) by weight from about 1% to about 6% (preferably by weight from about 2% to about 5%, more preferably by weight from
About 2% to the polymerizable components containing poly(ethylene glycol) about 4%), which includes at least one polymerizable groups, should
At least one polymerizable groups is acryloyl group ((OC (=O) CH ═ CH2), methylacryloyl (OC (=O) CCH3═CH2)、
Acrylamido (NHC (=O) CH ═ CH2), methacryl amido (NHC (=O) CCH3═CH2) or thiol group is (preferably
It is acryloyl group, methylacryloyl, acrylamido or methacryl amido group, more preferably acryloyl group or first
Base acryloyl group, even more preferably acryl group).
11. the device material as described in invention 10, wherein the polymerisable compound includes by weight from about 45% to about
At least one of 85% (more preferably by weight from about 50% to about 75%) contains poly- (phenyl with formula as defined above (IA)
Ether) monomer.
12. invention 10 or 11 as described in device material, wherein the polymerisable compound include by weight from about 2% to
The polymerizable components containing poly(ethylene glycol) of about 5% (more preferably by weight from about 2% to about 4%), the polymerizable components packet
Containing at least one polymerizable groups, which is acryloyl group ((OC (=O) CH ═ CH2), metering system
Acyl group (OC (=O) CCH3═CH2), acrylamido (NHC (=O) CH ═ CH2), methacryl amido (NHC (=O) CCH3
═CH2) or thiol group (preferably acryloyl group, methylacryloyl, acrylamido or methacryl amido base
Group, more preferably acryloyl group or methylacryloyl, even more preferably acryl group).
13. the device material as described in invention 12, wherein the polymerizable components for containing poly(ethylene glycol) include at least one
Polymerizable groups, at least one polymerizable groups are acryloyl group, methylacryloyl, acrylamido or metering system
Amide group (more preferably acryloyl group or methylacryloyl, even more preferably acryl group).
14. the device material as described in invention any one of 10 to 13, wherein it is described at least one containing poly- (phenyl ether)
Monomer is to be selected from the group consisting of:
And
15. the device material as described in invention any one of 10 to 14, the wherein polymerizable components for containing poly(ethylene glycol)
It is to be indicated by formula (II)
Wherein: A ' is H or CH3；Q and Q' is direct key, O, NH or C (=O) NHCH independently of one another2CH2O；X and X ' is only
It is on the spot direct key, O, NH, OC (=O) NH or NHC (=O) NH；R and R' is direct key or (CH independently of one another2)p；P=
1-3；M=2-6；G is H, C1-C4Alkyl, (CH2)mNH2、(CH2)mCO2Or R'-X'-Q'-C (=O) CA' ═ CH H,2；And work as G
=H, C1-C4Alkyl, (CH2)mNH2Or (CH2)mCO2When H, n=45-225；Otherwise n=51-225.
16. the device material as described in invention 15, wherein X and X' are direct key or O independently of one another in formula (II)；R
And R ' is direct key；Q and Q' is direct key or C (=O) NHCH independently of one another2CH2O；A ' is H or CH3；G is C1-C4Alkyl or
R'--X'-Q'--C (=O) CA ' ═ CH2；And work as G=C1-C4N=45-180 when alkyl；Otherwise n=51-225.
17. invention 15 or 16 as described in device material, wherein this have formula (II) containing the polymerizable of poly(ethylene glycol)
Component have 2,000-10,000 dalton (preferably 2,000-8,000 dalton, more preferable 2,000-6,000 dalton, and
Most preferably 2,500-6,000 dalton) number-average molecular weight.
18. the device material as described in any one of invention 1 to 17, wherein ophthalmic device material for manufacturing the present invention
The polymerisable compound further comprise by weight from about 10% to about 45% (preferably by weight from about 15% to about
40%, more preferably there are from about 20% to one or more about 35%) aryl acrylic monomers of formula (III) by weight
Wherein: A is H or CH3；B2It is (CH2)mOr [O (CH2)2]Z；M is 2-6；Z is 1-10；Y be direct key, O, S or
NR', condition are if Y is O, S or NR', and B is (CH2)m；R' is H, CH3、Cn'H2n'+1, iso- OC3H7、C6H5Or
CH2C6H5；N '=1-10；W is 0-6, and condition is m+w≤8；And D is H, Cl, Br, C1-C4Alkyl, C1-C4Alkoxy,
C6H5Or CH2C6H5。
19. invention 18 as described in device material, it is to be selected from the group that wherein this, which has the monomer of formula (III), the group by with
Lower every composition: acrylic acid 2- ethyl phenoxy group ester；Methacrylic acid 2- ethyl phenoxy group ester；Phenyl acrylate；Metering system
Acid phenenyl ester；Benzyl acrylate；Benzyl methacrylate；Acrylic acid 2- phenyl chlorocarbonate；Methacrylic acid 2- phenyl chlorocarbonate；Acrylic acid
3- phenylpropyl acrylate；Methacrylic acid 3- phenylpropyl acrylate；Acrylic acid 4- butyloxy phenyl；Methacrylic acid 4- butyloxy phenyl；Acrylic acid
4- methyl phenyl ester；Methacrylic acid 4- methyl phenyl ester；Acrylic acid 4- methyl benzyl ester；Methacrylic acid 4- methyl benzyl ester；Acrylic acid
2,2- aminomethyl phenyl ethyl ester；Methacrylic acid 2,2- aminomethyl phenyl ethyl ester；Acrylic acid 2,3- aminomethyl phenyl ethyl ester；Methacrylic acid
2,3- aminomethyl phenyl ethyl ester；Acrylic acid 2,4- aminomethyl phenyl ethyl ester；Methacrylic acid 2,4- aminomethyl phenyl ethyl ester；Acrylic acid 2-
(4- propyl phenyl) ethyl ester；Methacrylic acid 2- (4- propyl phenyl) ethyl ester；Acrylic acid 2- (4- (1- Methylethyl) phenyl) second
Ester；Methacrylic acid 2- (4- (1- Methylethyl) phenyl) ethyl ester；Acrylic acid 2- (4- methoxyphenyl) ethyl ester；Methacrylic acid
2- (4- methoxyphenyl) ethyl ester；Acrylic acid 2- (4- cyclohexyl phenyl) ethyl ester；Methacrylic acid 2- (4- cyclohexyl phenyl) second
Ester；Acrylic acid 2- (2- chlorphenyl) ethyl ester；Methacrylic acid 2- (2- chlorphenyl) ethyl ester；Acrylic acid 2- (3- chlorphenyl) ethyl ester；
Methacrylic acid 2- (3- chlorphenyl) ethyl ester；Acrylic acid 2- (4- chlorphenyl) ethyl ester；Methacrylic acid 2- (4- chlorphenyl) ethyl ester；
Acrylic acid 2- (4- bromophenyl) ethyl ester；Methacrylic acid 2- (4- bromophenyl) ethyl ester；Acrylic acid 2- (3- phenyl) ethyl ester；First
Base acrylic acid 2- (3- phenyl) ethyl ester；Acrylic acid 2- (4- phenyl) ethyl ester；Methacrylic acid 2- (4- phenyl)
Ethyl ester；Acrylic acid 2- (4- benzyl phenyl) ethyl ester；Methacrylic acid 2- (4- benzyl phenyl) ethyl ester；Acrylic acid 2- (thiophenyl) second
Ester；Methacrylic acid 2- (thiophenyl) ethyl ester；Acrylic acid 2- benzyloxy ethyl ester；Acrylic acid 3- benzyloxy propyl ester；Methacrylic acid
2- benzyloxy ethyl ester；Methacrylic acid 3- benzyloxy propyl ester；Acrylic acid 2- [2- (benzyloxy) ethyoxyl] ethyl ester；Methacrylic acid
2- [2- (benzyloxy) ethyoxyl] ethyl ester；And combinations thereof.
20. the device material as described in any one of invention 1 to 19, wherein the polymerisable compound further comprises having
The crosslinking agent and/or crosslinking agent selected from the group below containing poly- (phenyl ether) of formula (IB), the group consisting of: dimethyl propylene
Olefin(e) acid glycol ester；Diethyleneglycol dimethacrylate；Diethylene glycol dimethacrylate, dimethacrylate tetrem two
Alcohol ester, allyl methacrylate；Dimethacrylate 1,3- propylene glycol ester；Dimethacrylate 2,3- propylene glycol ester；Two
Methacrylic acid 1,6-HD ester；Dimethacrylate 1,4- butanediol ester；CH2=C (CH3) C (=O) O- (CH2CH2O)p-C
(=O) C (CH3)=CH2, wherein p=1-50；And CH2=C (CH3) C (=O) O (CH2)tO-C (=O) C (CH3)=CH2,
Middle t=3-20；And their corresponding acrylate.
21. the device material as described in invention 20, wherein the crosslinking agent is to be selected from the group consisting of:
CH2=C (CH3) C (=O) O- (CH2CH2O)p- C (=O) C- (CH3)=CH2, wherein p makes number average molecular weight be about 400, about
600 or about 1000；Ethylene glycol dimethacrylate (EGDMA)；Diethyleneglycol dimethacrylate；Dimethacrylate
Triglycol ester；Diacrylate triglycol ester；And diacrylate 1,4- butanediol ester (BDDA).
22. the device material as described in any one of invention 1 to 21, wherein the polymerisable compound further comprises one kind
Or a variety of polymerizable components selected from the group below, the group consisting of: polymerizable UV- absorbent, polymerizable coloured
Dyestuff, siloxanyl monomers, and combinations thereof.
23. the device material as described in invention 22, wherein the polymerisable compound further comprises the silicon with formula (IV)
Oxygen alkane monomer
Wherein: R2It is H or CH3；T is direct key, O (CH2)bOr OCH2CH(OH)CH2；B is 1-3；
J is (CH2)z；And K1、K2And K3It is independently CH3、C6H5Or OSi (CH3)3。
24. a kind of ophthalmology or otorhinolaryngologicdevice device comprising the device material as described in any one of invention 1 to 23.
25. ophthalmology or otorhinolaryngologicdevice device as described in invention 24, wherein the ophthalmology or otorhinolaryngologicdevice device are artificial crystalline substances
Shape body.
Foregoing disclosure will enable those of ordinary skill in the art to practice the present invention.In order to make reader be easier geography
Solve specific embodiment and its advantage, it is proposed that refer to following non-limiting example.However, following Examples should not be construed as limitation originally
The range of invention.
Example 1
The synthesis of 2- [4- (4- phenoxy-phenoxy) phenyl] ethyl alcohol
To 1L round-bottomed flask filling 4- phenoxy phenyl (95.0g, 0.51mol), THF (100mL), sodium hydroxide (24g,
0.6mol) and Dl water (80mL).The mixture is subjected to magnetic agitation in room temperature and continues 30 minutes, is then gone under reduced pressure
Except solvent.Then white solid is dried overnight at 150 DEG C under vacuum (70 millitorr), and be cooled to room temperature.Then
The bromo- 4- of 1- [2- (Phenylmethoxy) ethyl] benzene (150g, 0.51mol) and anhydrous pyridine (100mL) are added to the flask.It should
Mixture nitrogen purges 15 minutes, then adds stannous chloride (5g, 0.05mol).Then the mixture is blown again with nitrogen
15min is swept, and is then sealed under a nitrogen, and magnetic agitation one week in 130 DEG C of oil baths.Under vacuum removal pyridine it
Afterwards, crude product is dissolved in METHYLENE CHLORIDE (600mL), and with 2N HCI (200mL x 3), 2N NaOH (200mL x3)
It is washed.After removing solvent under reduced pressure, crude product is recrystallized from methanol/ethyl acetate (9/1, v/v).Then
10% palladium on carbon is used to hydrogenate as catalyst to product in THF in 100PSI, to provide crude product 2- [4- (4-
Phenoxy-phenoxy) phenyl] ethyl alcohol.Then the crude product is distilled under vacuum, then from hexane/ethyl acetate (1/
1, v/v) it recrystallizes, the product (122g, through two steps 78%) to provide as white crystal.
Acrylic acid 2- [4- (4- phenoxy-phenoxy) phenyl) ethyl ester (P3E2EA) synthesis:
2- [4- (4- phenoxy-phenoxy) phenyl] ethyl alcohol is loaded to the 1L three neck round bottom equipped with mechanical agitator
(61.2g, 0.2mol), anhydrous triethylamine (60mL, 0.42mol) and anhydrous methylene chlorine (300mL).By solution in ice salt
It is 15 minutes cooling under dry air covering in bath.Through 60min, acryloyl chloride (22mL, 0.27mol) is added by charging hopper
It is added in the cold soln being vigorously stirred, and being adjusted to keep the temperature of reaction mixture for adding speed is lower than 10 DEG C.?
After addition, reaction mixture is stirred in ice salt bath, continues two other hours, then passes through addition 2M HCI
(300mL) is quenched.The mixture is extracted with ethyl acetate (300mL x 3), and by combined organic layer DI
Water (200mL x 3), aqueous sodium bicarbonate (200mL x 2) washing, and use MgS04It is dry.It filters and removes under reduced pressure
Solvent provides the crude product in light brown oil, by its using hexane/ethyl acetate (9/1, v/v) as eluant, eluent on silica gel into
Row purifying, to provide the P3E2EA (62g, 86%) of white powder.
Example 2
The synthesis of acrylic acid 2- [2- (benzyloxy) ethyoxyl] ethyl ester (DEGMBA): to the 1L tri- equipped with mechanical agitator
Neck round-bottom flask loads diethylene glycol single-benzyl ether (98.0g, 0.5mol), anhydrous triethylamine (120mL, 0.85mol), Yi Jiwu
Water THF (300mL).Solution is 15 minutes cooling under dry air covering in ice salt bath.Through 90 minutes, leaked by charging
Acryloyl chloride (55mL, 0.68mol) is added in the cold soln being vigorously stirred by bucket, and adding speed is adjusted to keep anti-
The temperature for answering mixture is lower than 10 DEG C.After addition, reaction mixture is stirred in ice salt bath, is continued other
Two hours are then quenched by addition 2M HCI (400mL).The mixture is carried out with ethyl acetate (300mL x 3)
Extraction, and combined organic layer DI water (200mL x 3), aqueous sodium bicarbonate (200mL x 2) are washed, and used
MgS04It is dry.It filters and removal solvent provides the crude product in light brown oil under reduced pressure, it is used into hexane/ethyl acetate
(4/1, v/v) purified on silica gel as eluant, eluent, with provide be in colorless oil final product (105.0g, 0.42mol,
Yield: 84%).
Example 3
The polymer of crosslinking
Monomer from example 1 and example 2 is prepared as shown in table 1.It will measure at 55 DEG C with a thickness of 0.9mm's
Test sample is solidified 1 hour with blue light.Sample is extracted 20 hours in acetone at 55 DEG C, and then delayed at ambient temperature
Slow curing is dry to continue 20 hours, be placed in 70 DEG C of vacuum (1mm Hg) and continue minimum 20 hours.
Table 1
PTEA=acrylic acid 2- (thiophenyl) ethyl ester
PTEMA=methacrylic acid 2- (thiophenyl) ethyl ester
BDDA=diacrylate 1,4- butanediol ester
The polymer of poly- PEGMA=methacrylate sealing end, Mn=3,900, it is derived from PEG (350) monomethyl ether
Methacrylate
OMTP=2- (2H- benzo [d] [1,2,3] triazole -2- base) -4- methyl -6- (2- methacrylic) phenol
Blue blocking agent=N- [2- [4- hydroxyl -3- [2- (2- aminomethyl phenyl) diazenyl] phenyl] ethyl] metering system
Amide
Gorgeous good solid bis- (2,4,6- trimethylbenzoyl) phosphine oxides of 819=phenyl
The sample of above-mentioned preparation is hydrated in 23 DEG C of water-baths, and in 23 DEG C of measurement %EWC (equilibrium moisture content)
And refraction index.As a result it is reported in table 2.
The tensile properties of sample made above are also had evaluated as follows.It is cut using punch die and press machine from each sample sets
The lower stretching excellent sample in " dog bone " form.Typically, prepared by 3 samples for each slab, and matched for each
Product preparation amounts to 9 samples.Using 5543 extensometer of Instron with 500mm/min crosshead tachometric survey tensile properties.
Obtain fracture strength, breaking strain %, Young's modulus and 100% secant modulus data.As a result it shows in table 2.
By the way that three lens of each preparation are placed in the 20-mL bottle comprising about 20mL deionized water and are incited somebody to action
They, which are incubated in 45 DEG C of water-baths, continues 24 hours to measure anti-reflective photosensitiveness.Sample flasket is removed from water-bath, and is placed on
To be cooled to room temperature (typically 23 DEG C -24 DEG C) on experimental bench.After cooling to room-temperature, each lens are used into Olympus
(Olympus) BX60 microscope is imaged at bright field (BF) and dark field (DFA) setting in 10 times × 2 times amplifiers.
The weight percent of following measurement extractable matter.% is directed to each three-five polymer slabs for solidifying preparation
Extractable matter is weighed.At ambient temperature, polymer slab is extracted in acetone, continues at least 16 hours,
In a solvent is changed after first hour, and then covered and be dried in environment temperature with aluminium foil for 8 hours.By slab
It is further dried under reduced pressure at 60 DEG C and continues at least 16 hours.Slab is removed, and is cooled to room temperature (23 DEG C).It is right again
The slab previously weighed is weighed for % extractable matter.As a result it is reported in table 2.
Table 2
Claims (15)
1. a kind of polymerism ophthalmology or otorhinolaryngologicdevice device materials have at 589nm and 23 DEG C ± 3 DEG C at room temperature in complete water
Close 1.57 or the bigger refraction index, 60MPa or smaller Young's modulus, 35 DEG C or lower glass transition temperature of state measurement
Degree, at least 100% elongation, wherein the polymerism ophthalmology or otorhinolaryngologicdevice device materials be polymerisable compound copolymerization produce
Object, the polymerisable compound include a) by weight from 40% to 95% at least one with formula (IA) containing poly- (phenyl ether)
Monomer and b) by weight from 1% to 6% polymerizable components containing poly(ethylene glycol), which includes at least
One polymerizable groups, at least one polymerizable groups are acryloyl group (OC (=O) CH ═ CH2), methylacryloyl (OC
(=O) CCH3═CH2), acrylamido (NHC (=O) CH ═ CH2), methacryl amido (NHC (=O) CCH3═CH2) or
Thiol group,
Wherein:
R1It is H or CH3；
Ra、Rb、Rc、Rd、Re、Rf、Rg、RhAnd RiIt is H, C independently of one another1-C12Alkyl or C1-C12Alkoxy；
B1It is direct key, (CH2)m1Or (OCH2CH2)m2, wherein m1 is 2-6 and m2 is 1-10；
Q1It is direct key, O, NH or C (=O) NH (CH2)m3O, wherein m3 is the integer of 2-6；
N1 is from 1 to 9 integer；
N2 is from 0 to 6 integer；And
Y1It is direct key, O, S, OC (=O) NH, NHC (=O) NH or NR ', wherein R ' is H, C1-C10Alkyl, C6H5Or CH2C6H5。
2. device material as described in claim 1, wherein the device material is characterized by having in 589nm and at room temperature
1.58 or bigger refraction index, the Young's modulus from 1MPa to 45MPa, 30 DEG C or lower glass in the measurement of fully hydrated state
Glass transition temperature, at least 110% elongation.
3. device material as claimed in claim 1 or 2, wherein the polymerisable compound includes with formula (IB) containing poly-
The crosslinking agent of (phenyl ether):
Wherein:
R1And R1' it is H or CH independently of one another3；
Rj、Rk、Rl、Rm、Rn、Ro、RpAnd RqIt is H, C independently of one another1-C12Alkyl or C1-C12Alkoxy；
B1And B1' it is direct key, (CH independently of one another2)m1Or (OCH2CH2)m2, wherein m1 is 2-6 and m2 is 1-10；
Q1And Q1' it is direct key, O, NH or C (=O) NH (CH independently of one another2)m3O, wherein m3 is the integer of 2-6；
N2 and n2 ' is from 0 to 6 integer independently of one another；
N3 is from 1 to 100 integer；And
Y1And Y1' it is direct key, O, S, OC (=O) NH, NHC (=O) NH or NR ' independently of one another, wherein R ' is H, C1-C10Alkane
Base, C6H5Or CH2C6H5。
4. device material as claimed in any one of claims 1-3, wherein at least one monomer for containing poly- (phenyl ether)
Selected from the group being made of the following terms:
5. such as device material of any of claims 1-4, wherein the polymerizable components containing poly(ethylene glycol) by
Formula (II) indicates
Wherein: A ' is H or CH3；Q and Q' is direct key, O, NH or C (=O) NHCH independently of one another2CH2O；X and X ' are independently
It is direct key, O, NH, OC (=O) NH or NHC (=O) NH；R and R' is direct key or (CH independently of one another2)p；P=1-3；m
=2-6；G is H, C1-C4Alkyl, (CH2)mNH2、(CH2)mCO2Or R'-X'-Q'-C (=O) CA' ═ CH H,2；And when G=H,
C1-C4Alkyl, (CH2)mNH2Or (CH2)mCO2When H, n=45-225；Otherwise n=51-225.
6. device material as claimed in claim 5, wherein X and X' are direct key or O independently of one another in formula (II)；R and
R ' is direct key；Q and Q' is direct key or C (=O) NHCH independently of one another2CH2O；A ' is H or CH3；G is C1-C4Alkyl or
R'--X'-Q'--C (=O) CA ' ═ CH2；And work as G=C1-C4N=45-180 when alkyl；Otherwise n=51-225.
7. such as device material described in claim 5 or 6, wherein polymerizable group containing poly(ethylene glycol) with formula (II)
Divide the number-average molecular weight with 2,000-10,000 dalton.
8. the device material as described in any one of claims 1 to 7, wherein for manufacturing the described of the ophthalmic device material
Polymerisable compound further comprises by weight from 10% to 45% one or more aromatic substituted acrylic acids with formula (III)
Monomer
Wherein: A is H or CH3；B2It is (CH2)mOr [O (CH2)2]Z；M is 2-6；Z is 1-10；Y is direct key, O, S or NR', preceding
Mention is if Y is O, S or NR', B2It is (CH2)m；R' is H, CH3、Cn'H2n'+1, iso- OC3H7、C6H5Or CH2C6H5；N '=
1-10；W is 0-6, on condition that m+w≤8；And D is H, Cl, Br, C1-C4Alkyl, C1-C4Alkoxy, C6H5Or CH2C6H5。
9. device material as claimed in claim 8, wherein the monomer with formula (III) is selected from and is made of the following terms
Group: acrylic acid 2- ethyl phenoxy group ester；Methacrylic acid 2- ethyl phenoxy group ester；Phenyl acrylate；Phenyl methacrylate；Third
Olefin(e) acid benzyl ester；Benzyl methacrylate；Acrylic acid 2- phenyl chlorocarbonate；Methacrylic acid 2- phenyl chlorocarbonate；Acrylic acid 3- phenyl third
Ester；Methacrylic acid 3- phenylpropyl acrylate；Acrylic acid 4- butyloxy phenyl；Methacrylic acid 4- butyloxy phenyl；Acrylic acid 4- methylbenzene
Ester；Methacrylic acid 4- methyl phenyl ester；Acrylic acid 4- methyl benzyl ester；Methacrylic acid 4- methyl benzyl ester；Acrylic acid 2-2- methyl
Phenyl chlorocarbonate；Methacrylic acid 2,2- aminomethyl phenyl ethyl ester；Acrylic acid 2,3- aminomethyl phenyl ethyl ester；Methacrylic acid 2,3- methyl
Phenyl chlorocarbonate；Acrylic acid 2,4- aminomethyl phenyl ethyl ester；Methacrylic acid 2,4- aminomethyl phenyl ethyl ester；Acrylic acid 2- (4- propylbenzene
Base) ethyl ester；Methacrylic acid 2- (4- propyl phenyl) ethyl ester；Acrylic acid 2- (4- (1- Methylethyl) phenyl) ethyl ester；Methyl-prop
Olefin(e) acid 2- (4- (1- Methylethyl) phenyl) ethyl ester；Acrylic acid 2- (4- methoxyphenyl) ethyl ester；Methacrylic acid 2- (4- methoxy
Base phenyl) ethyl ester；Acrylic acid 2- (4- cyclohexyl phenyl) ethyl ester；Methacrylic acid 2- (4- cyclohexyl phenyl) ethyl ester；Acrylic acid
2- (2- chlorphenyl) ethyl ester；Methacrylic acid 2- (2- chlorphenyl) ethyl ester；Acrylic acid 2- (3- chlorphenyl) ethyl ester；Methacrylic acid
2- (3- chlorphenyl) ethyl ester；Acrylic acid 2- (4- chlorphenyl) ethyl ester；Methacrylic acid 2- (4- chlorphenyl) ethyl ester；Acrylic acid 2-
(4- bromophenyl) ethyl ester；Methacrylic acid 2- (4- bromophenyl) ethyl ester；Acrylic acid 2- (3- phenyl) ethyl ester；Methacrylic acid
2- (3- phenyl) ethyl ester；Acrylic acid 2- (4- phenyl) ethyl ester；Methacrylic acid 2- (4- phenyl) ethyl ester；Propylene
Sour 2- (4- benzyl phenyl) ethyl ester；Methacrylic acid 2- (4- benzyl phenyl) ethyl ester；Acrylic acid 2- (thiophenyl) ethyl ester；Methyl-prop
Olefin(e) acid 2- (thiophenyl) ethyl ester；Acrylic acid 2- benzyloxy ethyl ester；Acrylic acid 3- benzyloxy propyl ester；Methacrylic acid 2- benzyloxy second
Ester；Methacrylic acid 3- benzyloxy propyl ester；Acrylic acid 2- [2- (benzyloxy) ethyoxyl] ethyl ester；Methacrylic acid 2- [2- (benzyloxy
Base) ethyoxyl] ethyl ester；And combinations thereof.
10. device material as claimed in any one of claims 1-9 wherein, wherein the polymerisable compound further comprises power
Benefit requires the crosslinking agent and/or crosslinking agent selected from the group below containing poly- (phenyl ether) defined in 3, with formula (IB): diformazan
Base acrylic acid glycol ester；Diethyleneglycol dimethacrylate；Diethylene glycol dimethacrylate, dimethacrylate four
Glycol ester, allyl methacrylate；Dimethacrylate 1,3- propylene glycol ester；Dimethacrylate 2,3- propylene glycol
Ester；Dimethacrylate 1,6-HD ester；Dimethacrylate 1,4- butanediol ester；CH2=C (CH3) C (=O) O-
(CH2CH2O)p- C (=O) C (CH3)=CH2, wherein p=1-50；CH2=C (CH3) C (=O) O (CH2)tO-C (=O) C (CH3)
=CH2, wherein t=3-20；And their corresponding acrylate.
11. device material as claimed in claim 10, wherein the crosslinking agent is selected from the group being made of the following terms: CH2=C
(CH3) C (=O) O- (CH2CH2O)p- C (=O) C- (CH3)=CH2, wherein p makes number average molecular weight be 400；Dimethyl allene
Sour glycol ester (EGDMA)；Diethyleneglycol dimethacrylate；Diethylene glycol dimethacrylate；Three second of diacrylate
Diol ester；And diacrylate 1,4- butanediol ester (BDDA).
12. the device material as described in any one of claims 1 to 11, wherein the polymerisable compound further comprises one
Kind or a variety of polymerizable components selected from the group below: polymerizable UV- absorbent, polymerizable colored dyes, siloxanyl monomers and
A combination thereof.
13. device material as claimed in claim 12, wherein the polymerisable compound further comprises having formula (IV)
Siloxanyl monomers
Wherein: R2It is H or CH3；T is direct key or OCH2CH(OH)CH2；
J is (CH2)3；And K1、K2And K3It is independently CH3、C6H5Or OSi (CH3)3。
14. a kind of ophthalmology or otorhinolaryngologicdevice device comprising the device material as described in any one of claims 1 to 13.
15. ophthalmology as claimed in claim 14 or otorhinolaryngologicdevice device, wherein the ophthalmology or otorhinolaryngologicdevice device are artificial crystalline substances
Shape body.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201361911547P | 2013-12-04 | 2013-12-04 | |
| US61/911,547 | 2013-12-04 | ||
| PCT/US2014/068056 WO2015084788A1 (en) | 2013-12-04 | 2014-12-02 | Soft acrylic materials with high refractive index and minimized glistening |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105792860A CN105792860A (en) | 2016-07-20 |
| CN105792860B true CN105792860B (en) | 2019-06-04 |
Family
ID=52350290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480065465.3A Expired - Fee Related CN105792860B (en) | 2013-12-04 | 2014-12-02 | Reflective soft acrylic material with high refractive index and minimum |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US9289531B2 (en) |
| EP (1) | EP3077016B1 (en) |
| JP (1) | JP6166479B2 (en) |
| CN (1) | CN105792860B (en) |
| AU (1) | AU2014357334B2 (en) |
| CA (1) | CA2928011C (en) |
| ES (1) | ES2676743T3 (en) |
| WO (1) | WO2015084788A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106880848B (en) * | 2017-02-14 | 2019-09-06 | 四川大学 | Biodegradable poly HPMA-Gd magnetic resonance imaging probe and preparation method thereof |
| WO2018232025A1 (en) * | 2017-06-16 | 2018-12-20 | Yichieh Shiuey | Cell growth inhibiting copolymer for use in ophthalmic implants |
| JP2022522687A (en) | 2019-03-07 | 2022-04-20 | テレオン ホールディング ビー．ヴイ． | Intraocular lens composition |
| JP6799633B2 (en) * | 2019-04-24 | 2020-12-16 | 三菱瓦斯化学株式会社 | (Meta) Acrylic composition, paints and cured products containing it |
| US11708440B2 (en) | 2019-05-03 | 2023-07-25 | Johnson & Johnson Surgical Vision, Inc. | High refractive index, high Abbe compositions |
| AU2020270003A1 (en) | 2019-05-03 | 2020-12-03 | Johnson & Johnson Surgical Vision, Inc. | High reactive index, high abbe compositions |
| US11795252B2 (en) | 2020-10-29 | 2023-10-24 | Johnson & Johnson Surgical Vision, Inc. | Compositions with high refractive index and Abbe number |
Family Cites Families (47)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3162676A (en) | 1962-06-18 | 1964-12-22 | Nat Starch Chem Corp | Ethylenically unsaturated derivatives of 2, 4-dihydroxybenzophenone |
| US3299173A (en) | 1963-04-15 | 1967-01-17 | Diamond Alkali Co | Unsaturated polyesters prepared from reactable fire-retardant agents |
| US4304895A (en) | 1973-06-20 | 1981-12-08 | Wesley-Jessen, Inc. | Ultraviolet absorbing corneal contact lenses |
| US4528311A (en) | 1983-07-11 | 1985-07-09 | Iolab Corporation | Ultraviolet absorbing polymers comprising 2-hydroxy-5-acrylyloxyphenyl-2H-benzotriazoles |
| DE3439483A1 (en) | 1984-10-27 | 1986-05-07 | Röhm GmbH, 6100 Darmstadt | RADICALLY POLYMERIZABLE UV ABSORBER, METHOD FOR PRODUCING IT AND ITS POLYMERS |
| US4716234A (en) | 1986-12-01 | 1987-12-29 | Iolab Corporation | Ultraviolet absorbing polymers comprising 2-(2'-hydroxy-5'-acryloyloxyalkoxyphenyl)-2H-benzotriazole |
| US4834750A (en) | 1987-09-17 | 1989-05-30 | Ioptex Research, Inc. | Deformable-elastic intraocular lens |
| DE3842624A1 (en) | 1988-12-17 | 1990-06-21 | Bayer Ag | METHOD FOR PRODUCING BIFUNCTIONAL POLYPHENYLENE OXIDES WITH FINAL OH GROUPS |
| US5290892A (en) | 1990-11-07 | 1994-03-01 | Nestle S.A. | Flexible intraocular lenses made from high refractive index polymers |
| US5331073A (en) | 1992-11-09 | 1994-07-19 | Allergan, Inc. | Polymeric compositions and intraocular lenses made from same |
| US5470932A (en) | 1993-10-18 | 1995-11-28 | Alcon Laboratories, Inc. | Polymerizable yellow dyes and their use in opthalmic lenses |
| PT774983E (en) | 1995-06-07 | 2003-03-31 | Alcon Lab Inc | IMPROVED MATERIALS FOR OPHTHALMIC LENSES WITH HIGH REFRACTION INDEX |
| US5922821A (en) | 1996-08-09 | 1999-07-13 | Alcon Laboratories, Inc. | Ophthalmic lens polymers |
| US5891931A (en) | 1997-08-07 | 1999-04-06 | Alcon Laboratories, Inc. | Method of preparing foldable high refractive index acrylic ophthalmic device materials |
| US6353069B1 (en) | 1998-04-15 | 2002-03-05 | Alcon Manufacturing, Ltd. | High refractive index ophthalmic device materials |
| US6313187B2 (en) | 1998-04-15 | 2001-11-06 | Alcon Manufacturing, Ltd. | High refractive index ophthalmic device materials prepared using a post-polymerization cross-linking method |
| EP1080382B1 (en) | 1998-04-15 | 2009-07-08 | Alcon, Inc. | High refractive index ophthalmic device materials |
| DE69926364T2 (en) | 1998-04-15 | 2006-01-12 | Alcon Manufacturing Ltd., Fort Worth | MATERIAL FOR OPHTHALMOLOGICAL DEVICES WITH HIGH BREAKING INDEX MADE IN A PROCESS WITH NETWORKING THROUGH REVOLUTIONARYIZATION |
| CN1161158C (en) | 1998-04-15 | 2004-08-11 | 阿尔康实验室公司 | Coating composition for intraocular lens |
| US6241766B1 (en) | 1998-10-29 | 2001-06-05 | Allergan Sales, Inc. | Intraocular lenses made from polymeric compositions |
| US6245106B1 (en) | 1998-10-29 | 2001-06-12 | Allergan Sales, Inc. | Intraocular lenses made from polymeric compositions and monomers useful in said compositions |
| US6329485B1 (en) | 1998-12-11 | 2001-12-11 | Bausch & Lomb Incorporated | High refractive index hydrogel compositions for ophthalmic implants |
| US8247511B2 (en) * | 1999-04-12 | 2012-08-21 | Advanced Vision Science, Inc. | Water plasticized high refractive index polymer for ophthalmic applications |
| US6271281B1 (en) | 1999-08-26 | 2001-08-07 | Medennium, Inc. | Homopolymers containing stable elasticity inducing crosslinkers and ocular implants made therefrom |
| DK1210380T3 (en) * | 1999-09-07 | 2005-05-30 | Alcon Inc | Foldable ophthalmic and otorhinolaryngological device materials |
| US6703466B1 (en) | 2001-06-18 | 2004-03-09 | Alcon, Inc. | Foldable intraocular lens optics having a glassy surface |
| EP1521786B1 (en) | 2002-07-16 | 2008-04-23 | Alcon, Inc. | Ophthalmic and otorhinolaryngological device materials |
| US6872793B1 (en) | 2003-08-07 | 2005-03-29 | Alcon, Inc. | Ophthalmic and otorhinolaryngological device materials |
| US7652076B2 (en) | 2005-06-13 | 2010-01-26 | Alcon, Inc. | Ophthalmic and otorhinolaryngological device materials |
| EP1818690A1 (en) * | 2006-02-14 | 2007-08-15 | Procornea Holding B.V. | Intraocular lenses essentially free from glistenings |
| CA2652383C (en) * | 2006-06-01 | 2014-10-07 | Advanced Vision Science, Inc. | A non- or reduced glistenings intraocular lens and method of manufacturing same |
| US7714039B2 (en) | 2006-07-21 | 2010-05-11 | Alcon, Inc. | Low-tack ophthalmic and otorhinolaryngological device materials |
| TWI399228B (en) | 2006-07-21 | 2013-06-21 | Alcon Inc | Low-tack ophthalmic and otorhinolaryngological device materials |
| US8058323B2 (en) | 2006-07-21 | 2011-11-15 | Novartis Ag | Low-tack ophthalmic and otorhinolaryngological device materials |
| EP1905415B1 (en) | 2006-09-27 | 2009-07-01 | Ivoclar Vivadent AG | Polymerisable compositions comprising acyl-germanium as initiators |
| TWI449520B (en) | 2007-04-30 | 2014-08-21 | Alcon Inc | Ophthalmic and otorhinolaryngological device materials containing phenylene-siloxane macromers |
| WO2009015256A2 (en) | 2007-07-25 | 2009-01-29 | Alcon, Inc. | High refractive index ophthalmic device materials |
| TW200916130A (en) * | 2007-10-02 | 2009-04-16 | Alcon Inc | Ophthalmic and otorhinolaryngological device materials containing an alkylphenol ethoxylate |
| TWI426931B (en) | 2007-10-03 | 2014-02-21 | Alcon Inc | Ophthalmic and otorhinolaryngological device materials |
| TW201000155A (en) | 2008-05-06 | 2010-01-01 | Alcon Inc | High refractive index ophthalmic device materials |
| TWI453199B (en) | 2008-11-04 | 2014-09-21 | Alcon Inc | Uv/visible light absorbers for ophthalmic lens materials |
| US8362177B1 (en) | 2010-05-05 | 2013-01-29 | Novartis Ag | High refractive index ophthalmic device materials with reduced tack |
| TWI473823B (en) * | 2010-06-21 | 2015-02-21 | Novartis Ag | High refractive index, acrylic ophthalmic device materials with reduced glistenings |
| TWI517861B (en) * | 2011-02-08 | 2016-01-21 | 諾華公司 | Low-tack, hydrophobic ophthalmic device materials |
| TWI513768B (en) | 2011-06-01 | 2015-12-21 | Novartis Ag | Hydrophobic acrylic intraocular lens materials |
| TWI551646B (en) | 2011-06-03 | 2016-10-01 | 諾華公司 | Hydrophobic acrylic intraocular lens materials |
| WO2013122584A1 (en) * | 2012-02-15 | 2013-08-22 | Novartis Ag | Ophthalmic and otorhinolaryngological device materials containing a multi-arm peg macromer |
-
2014
- 2014-12-02 CN CN201480065465.3A patent/CN105792860B/en not_active Expired - Fee Related
- 2014-12-02 JP JP2016535698A patent/JP6166479B2/en active Active
- 2014-12-02 WO PCT/US2014/068056 patent/WO2015084788A1/en active Application Filing
- 2014-12-02 AU AU2014357334A patent/AU2014357334B2/en not_active Ceased
- 2014-12-02 ES ES14827588.6T patent/ES2676743T3/en active Active
- 2014-12-02 US US14/557,704 patent/US9289531B2/en active Active
- 2014-12-02 CA CA2928011A patent/CA2928011C/en not_active Expired - Fee Related
- 2014-12-02 EP EP14827588.6A patent/EP3077016B1/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| ES2676743T3 (en) | 2018-07-24 |
| EP3077016B1 (en) | 2018-05-16 |
| WO2015084788A1 (en) | 2015-06-11 |
| CA2928011C (en) | 2019-03-26 |
| AU2014357334A1 (en) | 2016-04-28 |
| EP3077016A1 (en) | 2016-10-12 |
| US20150151022A1 (en) | 2015-06-04 |
| AU2014357334B2 (en) | 2017-11-09 |
| CA2928011A1 (en) | 2015-06-11 |
| US9289531B2 (en) | 2016-03-22 |
| CN105792860A (en) | 2016-07-20 |
| JP6166479B2 (en) | 2017-07-19 |
| JP2017500930A (en) | 2017-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105792860B (en) | Reflective soft acrylic material with high refractive index and minimum | |
| EP2443485B1 (en) | Biomedical devices | |
| CN102946913B (en) | High refractive index, acrylic ophthalmic device materials with reduced glistenings | |
| CA2825359C (en) | Low-tack, hydrophobic ophthalmic device materials | |
| CN107206123A (en) | Wet packaging artificial crystalline lens material with high index of refraction | |
| EP2443484B1 (en) | Biomedical devices, polymeric materials and contact lenses comprising same. | |
| EP2443483B1 (en) | Multi-armed macromonomers, polymeric materials and contact lenses comprising same. | |
| EP2443482B1 (en) | Biomedical devices, polymeric materials and contact lenses comprising the same. | |
| KR20150023484A (en) | Polymers and nanogel materials and methods for making and using the same | |
| KR20140116882A (en) | Ionic silicone hydrogels | |
| AU2013266146A1 (en) | Polymers and nanogel materials and methods for making and using the same | |
| KR20140106734A (en) | Silicone hydrogels having a structure formed via controlled reaction kinetics | |
| KR20080026564A (en) | Ophthalmic and otorhinolaryngological device materials | |
| CN106999629B (en) | Low water content acrylate-acrylamide copolymers for ophthalmic devices | |
| JP6857784B2 (en) | Polymer material | |
| US20150353667A1 (en) | Flexible, high refractive index hydrophobic copolymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190604 Termination date: 20201202 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |